Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B15/00—Layered products comprising a layer of metal
  • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
  • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/36—After-treatment
  • C08J9/40—Impregnation
  • C08J9/42—Impregnation with macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/06—Polysulfones; Polyethersulfones

Definitions

• the present disclosure relates to polymer films and laminates.
• Japanese Unexamined Patent Application Publication No. 2016-102153 discloses a multiphase polymer material containing a filler, which has a co-continuous structure including at least a first phase and a second phase each having different properties.
• a multiphase polymer material (specifically, a conductive film) in which the filler is dispersed in a co-continuous structure so as to be unevenly distributed in a specific phase is described.
• the present disclosure has been made in view of such circumstances, and one embodiment of the present disclosure provides a polymer film with high toughness. Also, according to another embodiment of the present disclosure, a laminate using the above polymer film is provided.
• the present disclosure includes the following aspects.
• the first phase which is one of the at least two phases, contains a polymer having a glass transition temperature of 100 ° C. or higher, and among the at least two phases and the second phase different from the first phase contains at least one compound selected from the group consisting of a compound having a functional group and a compound having a bond A, wherein the bond A is a urethane bond , urea bond, amide bond, ester bond, ether bond, CC bond, NC bond, SC bond, and siloxane bond.
• the bond A is a urethane bond , urea bond, amide bond, ester bond, ether bond, CC bond, NC bond, SC bond, and siloxane bond.
• the first phase which has a phase-separated structure containing at least two phases and is one of the at least two phases, contains a liquid crystal polymer, is one of the at least two phases, and A second phase different from the first phase contains at least one compound selected from the group consisting of a compound having a functional group and a compound having a bond A, wherein the bond A is a urethane bond, a urea bond, an amide bond, A polymer film comprising at least one bond selected from the group consisting of an ester bond, an ether bond, a CC bond, an NC bond, an SC bond, and a siloxane bond.
• ⁇ 5> having a phase-separated structure containing at least two phases, the first phase being one of the at least two phases containing polysulfone, being one of the at least two phases, the first The second phase different from the phase contains at least one compound selected from the group consisting of a compound having a functional group and a compound having a bond A, wherein the bond A is a urethane bond, a urea bond, an amide bond, an ester A polymer film comprising at least one bond selected from the group consisting of a bond, an ether bond, a CC bond, an NC bond, an SC bond, and a siloxane bond.
• ⁇ 6> The polymer film according to any one of ⁇ 1> to ⁇ 5>, wherein the phase-separated structure is a co-continuous structure, a cylindrical structure, or a lamellar structure.
• Functional groups include (meth)acryloyl group, epoxy group, oxetanyl group, isocyanate group, acid anhydride group, carbodiimide group, N-hydroxyester group, glyoxal group, imidoester group, halogenated alkyl group, hydroxy group , a carboxy group, an amino group, an imidazole group, and a thiol group, the polymer film according to any one of ⁇ 1> to ⁇ 6>.
• Ar 4 and Ar 5 each independently represent a phenylene group or a naphthylene group, and Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group.
• Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group.
• ⁇ 10> Any one of ⁇ 1> to ⁇ 9>, further comprising at least one filler selected from the group consisting of boron nitride, aluminum nitride, graphite, silicon carbide, crystalline silica, alumina, and beryllium oxide
• ⁇ 11> The polymer film according to any one of ⁇ 1> to ⁇ 10>, further comprising a filler having a dielectric loss tangent of 0.01 or less.
• the filler is liquid crystal polymer particles, fluororesin particles, or an inorganic material.
• the inorganic material contains metal oxide particles.
• ⁇ 14> The polymer film according to ⁇ 12>, wherein the inorganic material contains fibers.
• ⁇ 15> A laminate comprising the polymer film according to any one of ⁇ 1> to ⁇ 14> and a metal layer or metal wiring disposed on at least one surface of the polymer film.
• ⁇ 16> The laminate according to ⁇ 15>, which has a metal layer and has a peel strength between the polymer film and the metal layer of 0.5 kN/m or more.
• a polymer film with high toughness can be provided. Further, according to another embodiment of the present disclosure, it is possible to provide a laminate using the polymer film.
• the term "to" indicating a numerical range is used to include the numerical values before and after it as lower and upper limits.
• the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step.
• the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
• alkyl group includes not only alkyl groups having no substituents (unsubstituted alkyl groups) but also alkyl groups having substituents (substituted alkyl groups).
• step in this specification is not only an independent step, but even if it cannot be clearly distinguished from other steps, if the intended purpose of the step is achieved included.
• % by mass and % by weight are synonymous, and “parts by mass” and “parts by weight” are synonymous.
• the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation). It is a molecular weight converted using polystyrene as a standard substance detected with a solvent THF (tetrahydrofuran) and a differential refractometer using a gel permeation chromatography (GPC) analyzer.
• a "(meth)acryloyl group” includes both an acryloyl group and a methacryloyl group.
• a first aspect of the polymer film according to the present disclosure has a phase separation structure including at least two phases, and the first phase, which is one of the at least two phases, is a polymer having a glass transition temperature of 100 ° C. or higher wherein the second phase, which is one of at least two phases and is different from the first phase, comprises at least one selected from the group consisting of a compound having a functional group and a compound having a bond A , bond A is at least one bond selected from the group consisting of urethane bond, urea bond, amide bond, ester bond, ether bond, CC bond, NC bond, SC bond, and siloxane bond be.
• a second aspect of the polymer film according to the present disclosure has a phase-separated structure comprising at least two phases, wherein the first phase, one of the at least two phases, comprises a liquid crystalline polymer, the at least two phases
• the second phase which is one of and different from the first phase, contains at least one compound selected from the group consisting of a compound having a functional group and a compound having a bond A, wherein the bond A is At least one bond selected from the group consisting of a urethane bond, a urea bond, an amide bond, an ester bond, an ether bond, a CC bond, an NC bond, an SC bond, and a siloxane bond.
• a third aspect of the polymer film according to the present disclosure has a phase-separated structure comprising at least two phases, a first phase being one of the at least two phases comprising polysulfone,
• the second phase one of which is different from the first phase, contains at least one compound selected from the group consisting of a compound having a functional group and a compound having a bond A, wherein the bond A is urethane It is at least one bond selected from the group consisting of a bond, a urea bond, an amide bond, an ester bond, an ether bond, a CC bond, an NC bond, an SC bond, and a siloxane bond.
• the first phase includes a polymer having a glass transition temperature of 100° C. or higher
• the second phase includes a compound having a functional group and a compound having a bond A. Since it contains at least one selected from the group consisting of, toughness is higher than before.
• the toughness is higher than the conventional one.
• one phase contains styrene-butadiene rubber (SBR), styrene-ethylene/butylene-styrene copolymer (SEBS), and the like. contained and had insufficient toughness.
• SBR styrene-butadiene rubber
• SEBS styrene-ethylene/butylene-styrene copolymer
• phase-separated structure means a structure in which at least two portions containing different components are present in the polymer film.
• a film having a phase-separated structure is preferably formed by transforming a single phase into two or more distinct phases during the manufacturing process. For example, in solution casting, a film having a phase-separated structure is formed from a homogeneous solution, and a film having a phase-separated structure is formed by applying energy such as heat and pressure to a homogeneous film. mentioned.
• the phase separation structure includes, for example, a sea-island structure, a co-continuous structure, a cylinder structure, and a lamellar structure.
• the sea-island structure means a structure in which one of at least two phases forms a continuous phase and the other phases are dispersed discontinuously.
• a co-continuous structure means a structure in which at least two phases both form a continuous phase.
• a cylindrical structure means a structure having a plurality of rod-like phases in at least one of at least two phases.
• a lamellar structure means a layered structure in which at least two phases are alternately stacked. Both the cylindrical structure and the lamellar structure are structures in which at least two phases form a continuous phase. .
• the polymer film according to the present disclosure preferably has a phase-separated structure in which at least two phases form continuous phases.
• the phase-separated structure in the polymer film according to the present disclosure is preferably a co-continuous structure, a cylindrical structure, or a lamellar structure.
• Having a phase separation structure can be confirmed by using morphological observation for the film surface, the film cross section, or both the film surface and the cross section. If it cannot be confirmed by morphological observation, it can be confirmed by using material distribution evaluation means. If it cannot be confirmed by material distribution evaluation, it can be confirmed by using mechanical property distribution evaluation means. Morphological observation can be performed using a known optical microscope. If it cannot be confirmed with an optical microscope, it can be performed using an electron microscope or the like. Material distribution evaluation can use infrared spectroscopy. If infrared spectroscopy cannot be used, Raman spectroscopy can be used. If it cannot be confirmed by Raman spectroscopy, it can be performed using imaging such as an X-ray photoelectron spectroscopy analyzer. A mechanical property distribution evaluation can be performed using an atomic force microscope.
• a polymer film according to the present disclosure has a phase-separated structure comprising at least two phases.
• a first phase one of the at least two phases, comprises a polymer with a glass transition temperature of 100° C. or higher.
• the glass transition temperature of the polymer contained in the first phase is preferably 120° C. or higher, more preferably 150° C. or higher.
• the upper limit of the glass transition temperature is not particularly limited, it is preferably 300° C. from the viewpoint of moldability.
• the glass transition temperature Tg can be measured using a differential scanning calorimetry (DSC) device. 5 mg of a sample was placed in a DSC measurement pan, and the temperature was raised from 30°C at 10°C/min in a nitrogen stream. can be Combinations of the two phases may result in more than one Tg. If it cannot be measured by differential scanning calorimetry, a film cross-section sample prepared by cutting the film surface with a microtome is scanned with a scanning probe microscope (product name "SPA400", manufactured by SII Nanotechnology Co., Ltd.). It is also possible to obtain Tg from changes in storage elastic modulus or loss tangent (loss elastic modulus/storage elastic modulus) with respect to measurement temperature by observation in VE-AFM mode.
• DSC differential scanning calorimetry
• polymers having a glass transition temperature of 100° C. or higher include liquid crystal polymers, polyesters, polycarbonates, acrylic resins, polystyrenes, polyolefins, polyamides, polyimides, polysulfones, polyethersulfones, polyetheretherketones, polyphenylene sulfides, polyvinyl alcohols, poly Examples include vinylidene chloride, epoxy resins, and fluororesins.
• the polymer having a glass transition temperature of 100°C or higher is preferably a liquid crystal polymer or polysulfone.
• liquid crystal polymer The type of liquid crystal polymer is not particularly limited, and known liquid crystal polymers can be used. Further, the liquid crystal polymer may be a thermotropic liquid crystal polymer that exhibits liquid crystallinity in a molten state, or a lyotropic liquid crystal polymer that exhibits liquid crystallinity in a solution state. In the case of thermotropic liquid crystal, it is preferable that it melts at a temperature of 450° C. or less.
• liquid crystalline polymers examples include liquid crystalline polyesters, liquid crystalline polyester amides in which amide bonds are introduced into liquid crystalline polyesters, liquid crystalline polyester ethers in which ether bonds are introduced into liquid crystalline polyesters, and liquid crystalline polyester carbonates in which carbonate bonds are introduced into liquid crystalline polyesters. is mentioned.
• the liquid crystal polymer is preferably a polymer having an aromatic ring, more preferably an aromatic polyester or an aromatic polyesteramide, and even more preferably an aromatic polyesteramide.
• the liquid crystal polymer may be a polymer in which an isocyanate-derived bond such as an imide bond, a carbodiimide bond, or an isocyanurate bond is introduced into an aromatic polyester or an aromatic polyester amide.
• an isocyanate-derived bond such as an imide bond, a carbodiimide bond, or an isocyanurate bond is introduced into an aromatic polyester or an aromatic polyester amide.
• liquid crystal polymer is preferably a wholly aromatic liquid crystal polymer that uses only aromatic compounds as raw material monomers.
• liquid crystal polymers include, for example: 1) (i) an aromatic hydroxycarboxylic acid, (ii) an aromatic dicarboxylic acid, and (iii) at least one compound selected from the group consisting of an aromatic diol, an aromatic hydroxylamine and an aromatic diamine; A product obtained by polycondensation. 2) Those obtained by polycondensing a plurality of types of aromatic hydroxycarboxylic acids. 3) Polycondensation of (i) an aromatic dicarboxylic acid and (ii) at least one compound selected from the group consisting of aromatic diols, aromatic hydroxylamines and aromatic diamines.
• Examples of polymerizable derivatives of compounds having a carboxy group such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids include those obtained by converting the carboxy group to an alkoxycarbonyl group or an aryloxycarbonyl group (ester), carboxy Examples thereof include those obtained by converting a group to a haloformyl group (acid halides) and those obtained by converting a carboxy group to an acyloxycarbonyl group (acid anhydrides).
• Examples of polymerizable derivatives of compounds having a hydroxy group such as aromatic hydroxycarboxylic acids, aromatic diols and aromatic hydroxyamines include those obtained by acylating the hydroxy group to convert it to an acyloxy group (acylated product). is mentioned.
• Examples of polymerizable derivatives of compounds having an amino group such as aromatic hydroxylamines and aromatic diamines include those obtained by acylating the amino group to convert it to an acylamino group (acylated product).
• the liquid crystal polymer is a structural unit represented by any of the following formulas (1) to (3) (hereinafter, the structural unit represented by the formula (1), etc. It is preferable to have a structural unit represented by the following formula (1), and it is more preferable to have a structural unit represented by the following formula (1), and a structural unit represented by the following formula (2). and a structural unit represented by the following formula (2).
• Ar 1 represents a phenylene group, naphthylene group or biphenylylene group
• Ar 2 and Ar 3 each independently represent a phenylene group, naphthylene group, biphenylylene group or the following formula (4) represents a group represented by X and Y each independently represents an oxygen atom or an imino group
• hydrogen atoms in the groups represented by Ar 1 to Ar 3 each independently represent a halogen atom, an alkyl group Alternatively, it may be substituted with an aryl group.
• Ar 4 and Ar 5 each independently represent a phenylene group or a naphthylene group, and Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, or an alkylene group.
• the halogen atoms include fluorine, chlorine, bromine and iodine atoms.
• alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group and n-decyl group, preferably having 1 to 10 carbon atoms.
• aryl group examples include phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 1-naphthyl group and 2-naphthyl group, preferably having 6 to 20 carbon atoms. be.
• the number thereof is preferably 2 or less, more preferably 1, independently for each of the above groups represented by Ar 1 , Ar 2 or Ar 3 . is one.
• alkylene group examples include methylene group, 1,1-ethanediyl group, 1-methyl-1,1-ethanediyl group, 1,1-butanediyl group and 2-ethyl-1,1-hexanediyl group. , preferably has 1 to 10 carbon atoms.
• Unit (1) is a structural unit derived from a predetermined aromatic hydroxycarboxylic acid.
• Unit (1) includes those in which Ar 1 is a p-phenylene group (structural unit derived from p-hydroxybenzoic acid) and those in which Ar 1 is a 2,6-naphthylene group (6-hydroxy-2 - structural unit derived from naphthoic acid) or a 4,4'-biphenylylene group (structural unit derived from 4'-hydroxy-4-biphenylcarboxylic acid).
• Unit (2) is a structural unit derived from a predetermined aromatic dicarboxylic acid.
• Unit (2) includes those in which Ar 2 is a p-phenylene group (structural unit derived from terephthalic acid), those in which Ar 2 is an m-phenylene group (structural unit derived from isophthalic acid), and those in which Ar 2 is 2,6-naphthylene group (structural unit derived from 2,6-naphthalene dicarboxylic acid), or Ar 2 is diphenyl ether-4,4'-diyl group (diphenyl ether-4,4'-dicarboxylic acid Structural units derived from acids) are preferred.
• Unit (3) is a structural unit derived from a predetermined aromatic diol, aromatic hydroxylamine or aromatic diamine.
• Unit (3) includes those in which Ar 3 is a p-phenylene group (structural units derived from hydroquinone, p-aminophenol, or p-phenylenediamine), those in which Ar 3 is an m-phenylene group (constitutional units derived from isophthalic acid). derived structural unit), or those in which Ar 3 is a 4,4'-biphenylylene group (derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl structural unit) is preferred.
• the content of unit (1) is the total amount of all structural units (the mass of each structural unit constituting the liquid crystal polymer is divided by the formula weight of each unit, and the equivalent amount (mol) of each unit is obtained. , the total value thereof), preferably 30 mol% or more, more preferably 30 mol% to 80 mol%, still more preferably 30 mol% to 60 mol%, particularly preferably 30 mol% to 40 mol% is.
• the content of unit (2) is preferably 35 mol% or less, more preferably 10 mol% to 35 mol%, still more preferably 20 mol% to 35 mol%, particularly preferably 35 mol% or less, based on the total amount of all structural units. is 30 mol % to 35 mol %.
• the content of unit (3) is preferably 35 mol% or less, more preferably 10 mol% to 35 mol%, still more preferably 20 mol% to 35 mol%, particularly preferably 35 mol% or less, based on the total amount of all structural units. is 30 mol % to 35 mol %.
• the ratio between the content of units (2) and the content of units (3) is expressed by [content of units (2)]/[content of units (3)] (mol/mol), preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, still more preferably 0.98/1 to 1/0.98.
• the liquid crystal polymer may have two or more types of units (1) to (3) each independently. Further, the liquid crystal polymer may have constitutional units other than the units (1) to (3).
• the content of structural units other than units (1) to (3) is preferably 10 mol % or less, more preferably 5 mol % or less, relative to the total amount of all units.
• the lower limit of the content is not particularly limited, and may be 0 mol %.
• the liquid crystal polymer has units (3) in which at least one of X and Y is an imino group, i.e., at least It is preferable to have one of them because the solubility in a solvent is excellent, and it is more preferable to have only units in which at least one of X and Y is an imino group as the unit (3).
• the liquid crystal polymer is preferably produced by melt-polymerizing raw material monomers corresponding to the structural units that constitute it.
• the melt polymerization may be carried out in the presence of a catalyst, examples of which include metal compounds such as magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, potassium acetate, antimony trioxide, Nitrogen-containing heterocyclic compounds such as 4-(dimethylamino)pyridine and 1-methylimidazole are included, and nitrogen-containing heterocyclic compounds are preferably used.
• the melt polymerization may be further subjected to solid phase polymerization, if necessary.
• the liquid crystal polymer has a flow initiation temperature of preferably 250°C or higher, more preferably 250°C or higher and 350°C or lower, and still more preferably 260°C or higher and 330°C or lower.
• a flow initiation temperature of the liquid crystal polymer is within the above range, the solubility, heat resistance, strength and rigidity are excellent, and the viscosity of the solution is moderate.
• the flow initiation temperature is also called flow temperature or flow temperature, and melts the liquid crystal polymer while increasing the temperature at a rate of 4 ° C./min under a load of 9.8 MPa (100 kg/cm 2 ) using a capillary rheometer. It is the temperature at which a viscosity of 4,800 Pa s (48,000 poise) is exhibited when extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm, and is a measure of the molecular weight of a liquid crystal polymer (edited by Naoyuki Koide). , "Liquid Crystal Polymer -Synthesis/Molding/Application-", CMC Co., Ltd., June 5, 1987, p.95).
• the weight average molecular weight of the liquid crystal polymer is preferably 1,000,000 or less, more preferably 3,000 to 300,000, even more preferably 5,000 to 100,000, 5,000 to 30,000 are particularly preferred.
• the heat-treated film is excellent in thermal conductivity, heat resistance, strength and rigidity in the thickness direction.
• the content of the polymer having a glass transition temperature of 100° C. or higher is preferably 50% by volume or more, more preferably 80% by volume or more, and 90% by volume or more, relative to the total volume of the first phase. is more preferred.
• the upper limit of the content of the polymer having a glass transition temperature of 100° C. or higher is not particularly limited, and may be 100% by volume. That is, the first phase may consist only of a polymer having a glass transition temperature of 100° C. or higher.
• the dielectric loss tangent of the polymer having a glass transition temperature of 100°C or higher is 0.01 or lower.
• the dielectric loss tangent of the polymer is preferably 0.005 or less, more preferably 0.004 or less, still more preferably 0.0035 or less, and particularly more than 0 and 0.003 or less preferable.
• polymers having a dielectric loss tangent of 0.01 or less include liquid crystal polymers, fluorine-based polymers, polymers of compounds having a cycloaliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, polyether ether ketones, Thermoplastic resins such as polyolefins, polyamides, polyesters, polyphenylene sulfides, polyetherketones, polycarbonates, polyethersulfones, polyphenylene ethers and modified products thereof, and polyetherimides; elastomers such as copolymers of glycidyl methacrylate and polyethylene; phenolic resins , epoxy resins, polyimides, and cyanate resins.
• liquid crystal polymers such as polyolefins, polyamides, polyesters, polyphenylene sulfides, polyetherketones, polycarbonates, polyethersulfones, polyphenylene ethers and modified products thereof, and polyetherimi
• the polymer is a liquid crystal polymer, a fluorine-based polymer, a polymer of a compound having a cyclic aliphatic hydrocarbon group and a group having an ethylenically unsaturated bond, and a polyether ether It is preferably at least one selected from the group consisting of ketones, and more preferably at least one selected from the group consisting of liquid crystal polymers and fluoropolymers, from the viewpoint of film formability and mechanical strength. , a liquid crystal polymer is particularly preferable, and from the viewpoint of dielectric loss tangent, a fluorine-based polymer is particularly preferable.
• the method for measuring the dielectric loss tangent in the present disclosure shall be measured by the following method. Loss tangent measurements are performed by the resonance perturbation method at a frequency of 10 GHz. A 10 GHz cavity resonator (Kanto Electronics Applied Development Co., Ltd. CP531) is connected to a network analyzer (Agilent Technology "E8363B"), and a measurement sample (width: 2.0 mm x length: 80 mm) is inserted into the cavity resonator. Then, the dielectric loss tangent of the measurement sample is measured from the change in resonance frequency before and after insertion for 96 hours under an environment of temperature 25° C. and humidity 60% RH.
• the first phase may further contain other components such as fillers, plasticizers, antioxidants, UV absorbers, flame retardants, colorants, antifoaming agents and surfactants.
• a polymer film according to the present disclosure has a phase-separated structure comprising at least two phases.
• the second phase which is one of the at least two phases and is different from the first phase, contains at least one selected from the group consisting of a compound having a functional group and a compound having a bond A.
• the compound having a functional group is not particularly limited except that it has a functional group, and can be selected as appropriate.
• the functional group is a (meth)acryloyl group, an epoxy group, an oxetanyl group, an isocyanate group, an acid anhydride group, a carbodiimide group, an N-hydroxyester group, a glyoxal group, an imidoester group, and an alkyl halide. It is preferably at least one selected from the group consisting of a group, a hydroxy group, a carboxy group, an amino group, an imidazole group, and a thiol group, and more preferably an epoxy group.
• the compound having a functional group may be a low-molecular-weight compound with a molecular weight of less than 1,000, or a high-molecular-weight compound with a weight-average molecular weight Mw of 1,000 or more.
• Examples of functional groups that can react with epoxy groups include amino groups, imidazole groups, and acid anhydride groups.
• the compound having a functional group preferably contains an epoxy resin and a curing agent for the epoxy resin.
• Curing agents for epoxy resins include, for example, amines, imidazole compounds, phenol resins, and amino resins. Among them, the epoxy resin curing agent is preferably an imidazole compound. Epoxy resins and imidazole compounds generally do not undergo a curing reaction at room temperature, so the timing of curing can be adjusted.
• the compound having bond A is not particularly limited except that it has bond A, and can be selected as appropriate.
• the bond A is selected from the group consisting of a urethane bond, a urea bond, an amide bond, an ester bond, an ether bond, a C-C bond, a N-C bond, an S-C bond, and a siloxane bond. at least one bond that Among them, the bond A is preferably an NC bond.
• the compound having bond A preferably contains a structure represented by —CH 2 —CH(OH)—, and more preferably includes a structure represented by >N—CH 2 —CH(OH)—. preferable.
• the second phase may further contain other components such as fillers, plasticizers, antioxidants, UV absorbers, flame retardants, colorants, antifoaming agents, and surfactants.
• the polymer film according to the present disclosure may contain fillers.
• the polymer film may contain only one type of filler, or may contain two or more types.
• the filler may be contained in only a part of the at least two phases, or may be contained in all the phases.
• the filler is preferably contained in the second phase. That is, the second phase preferably contains at least one selected from the group consisting of a compound having a functional group and a compound having a bond A, and a filler.
• the filler may be particulate (eg, inorganic particles) or fibrous (eg, inorganic fibers). Further, the filler may be an inorganic filler or an organic filler.
• the filler may have a low dielectric loss tangent, low dielectric constant, high dielectric constant, high thermal conductivity, high hardness, and high elastic modulus, and may be electrically insulating, semiconductive, or conductive.
• the volume resistivity of the filler is preferably 1.0 ⁇ 10 11 ⁇ cm or more, more preferably 3.0 ⁇ 10 11 ⁇ cm or more. It is preferably 1.0 ⁇ 10 12 ⁇ cm or more, and particularly preferably 1.0 ⁇ 10 12 ⁇ cm or more.
• the upper limit of the volume resistivity is not particularly limited, but is practically 1.0 ⁇ 10 18 ⁇ cm.
• the volume resistivity of the filler is not particularly limited, but is practically 1.0 ⁇ 10 ⁇ 7 ⁇ cm or more. Also, the volume resistivity is preferably less than 1.0 ⁇ 10 11 ⁇ cm.
• the thermal diffusivity of the filler is, for example, 1.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more, preferably 2.0 ⁇ 10 ⁇ 6 m 2 s ⁇ 1 or more, and 3.0 ⁇ 10 ⁇ Particularly preferably, it is 6 m 2 s ⁇ 1 or more.
• the upper limit of the thermal diffusivity of the filler is not particularly limited, it is practically 1.0 ⁇ 10 ⁇ 4 m 2 s ⁇ 1 .
• the density of the filler is, for example, 4.0 g/cm 3 or less, more preferably 3.0 g/cm 3 or less.
• the lower limit of the filler density is not particularly limited, but is practically 1.0 g/cm 3 .
• the density of the filler means the density of the solid content constituting the filler.
• inorganic filler can be used as the inorganic filler.
• inorganic filler materials include metal oxides, metal hydroxides, metal carbonates, metal nitrides, silicon compounds, boron compounds, carbon compounds, and composite compounds thereof.
• inorganic filler materials include boron nitride, aluminum nitride, silicon nitride, titanium oxide, magnesium oxide, zinc oxide, copper oxide, cuprous oxide, silica, alumina, beryllium oxide, barium titanate, and strontium titanate.
• the inorganic filler may be glass fiber, carbon fiber (pitch-based, PAN-based), carbon nanotube (CNT), carbon nanofiber (CNF), rock fiber, slag fiber, or metal fiber.
• a well-known organic filler can be used as an organic filler.
• Materials for the organic filler include, for example, liquid crystal polymer, polyethylene, polystyrene, urea-formalin filler, polyester, cellulose, acrylic resin, fluorine resin, hardened epoxy resin, crosslinked benzoguanamine resin, and crosslinked acrylic resin.
• the organic filler may be nanofiber cellulose.
• the polymer film according to the present disclosure is a group consisting of boron nitride, aluminum nitride, graphite, silicon carbide, silica, alumina, and beryllium oxide. It is preferable to include at least one filler selected from among others.
• the filler may be configured by coating or surface-treating semiconductive or conductive thermally conductive particles with an electrically insulating material such as silica. According to such an aspect, it becomes easy to control the thermal conductivity and the electrical insulation individually, so that the adjustment of the thermal conductivity and the electrical insulation becomes easy.
• methods for forming a silica film on the surface include a water glass method and a sol-gel method.
• fillers may be used singly or in combination of two or more.
• the shape of the filler is not particularly limited, and examples thereof include fibrous, plate-like, scale-like, rod-like, spherical, tube-like, curved plate-like, and needle-like shapes.
• the filler may be subjected to surface treatments such as silane coupling treatment, titanate coupling treatment, epoxy treatment, urethane treatment, and oxidation treatment.
• surface treatment agents used for surface treatment include polyol, aluminum oxide, aluminum hydroxide, silica (silicon oxide), hydrous silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogen dimethicone, and silane coupling agents.
• the surface treatment agent is preferably a silane coupling agent.
• the average primary particle size of the filler is preferably 0.0130 ⁇ m to 30 ⁇ m.
• the lower limit of the average primary particle size of the filler is more preferably 0.05 ⁇ m, more preferably 0.1 ⁇ m, and particularly preferably 0.3 ⁇ m.
• the upper limit of the average primary particle size of the filler is more preferably 20 ⁇ m, more preferably 15 ⁇ m, and particularly preferably 10 ⁇ m.
• the filler may contain a particulate mixture in which at least two kinds of particle groups having different average primary particle sizes are mixed. This arrangement embeds the smaller particles between the larger particles, reducing the spacing between the fillers and thus increasing the points of contact as compared to having only single size fillers.
• the peak particle size ratio (the ratio of particle sizes corresponding to peak apexes) is preferably 1.5-50.
• the lower limit of the peak particle size ratio is preferably 2, more preferably 4.
• the upper limit of the peak particle size ratio is preferably 40, more preferably 20.
• the polymer film according to the present disclosure preferably contains a filler with a dielectric loss tangent of 0.01 or less. More preferably, the dielectric loss tangent is 0.005 or less.
• the lower limit of the dielectric loss tangent is not particularly limited, and is, for example, 0.002.
• the filler is preferably liquid crystal polymer particles, fluororesin particles, or an inorganic material. From the viewpoint of reducing the dielectric loss tangent, the inorganic material preferably contains metal oxide particles. Moreover, the inorganic material preferably contains fibers from the viewpoint of reducing the dielectric loss tangent.
• the average particle diameter of the filler is preferably 5 nm to 20 ⁇ m, more preferably 10 nm to 1 ⁇ m, even more preferably 20 nm to 500 nm, and even more preferably 25 nm to 25 nm, from the viewpoint of improving electrical properties and thermal conductivity. 90 nm is particularly preferred.
• the content of the filler contained in one of the at least two phases is 20% by volume or more with respect to the total volume of either phase. It is preferably 30% by volume or more, more preferably 30% by volume or more.
• the upper limit of the filler content in any phase is not particularly limited, and is, for example, 80% by volume.
• the polymer film according to the present disclosure may contain additives other than the polymer and filler.
• additives known additives can be used. Specific examples include leveling agents, antifoaming agents, antioxidants, ultraviolet absorbers, flame retardants, colorants and the like.
• the polymer film according to the present disclosure preferably has a thermal conductivity of 1 W/(m ⁇ K) or more, more preferably 3 W/(m ⁇ K) or more.
• the upper limit of thermal conductivity is not particularly limited, and is, for example, 20 W/(m ⁇ K).
• Thermal conductivity is measured by the following method.
• the thermal conductivity in the thickness direction is measured using a thermal conductivity measuring device (product name: "TCM-1000", manufactured by Lesca).
• the average thickness of the polymer film according to the present disclosure is preferably 6 ⁇ m to 200 ⁇ m, more preferably 12 ⁇ m to 100 ⁇ m, and particularly preferably 20 ⁇ m to 60 ⁇ m.
• the average thickness of the polymer film is measured at any five locations using an adhesive film thickness gauge, for example, an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and the average value thereof is taken.
• an adhesive film thickness gauge for example, an electronic micrometer (product name "KG3001A", manufactured by Anritsu Corporation), and the average value thereof is taken.
• the dielectric loss tangent of the polymer film according to the present disclosure is preferably 0.005 or less, more preferably more than 0 and 0.003 or less.
• a method for producing a polymer film according to the present disclosure includes, for example, the following steps.
• (1) A first solution prepared by dissolving a polymer having a glass transition temperature of 100° C. or higher and a compound incompatible with the polymer having a glass transition temperature of 100° C. or higher in a solvent is cast on a support to form a membrane A.
• Process (casting process) (2) Step of immersing film A in a coagulation bath to form film B (immersion step) (3) A step of eluting a compound incompatible with a polymer having a glass transition temperature of 100° C. or higher from membrane B to prepare a porous membrane (elution step).
• (4) Step of baking the porous membrane (baking step) (5) Step of impregnating the baked porous membrane with a second solution containing a compound having a functional group (impregnation step)
• a polymer having a glass transition temperature of 100° C. or higher and a first solution obtained by dissolving a compound incompatible with the polymer having a glass transition temperature of 100° C. or higher in a solvent are cast onto a support to form the membrane A. It is a process of forming.
• the casting method in the casting step is not particularly limited, and known casting methods can be used.
• the casting temperature and casting speed are not particularly limited, and may be determined with reference to known casting methods and the composition of the solution used.
• the average thickness of the membrane A is not particularly limited as long as it is a desired thickness. More preferably 50 ⁇ m to 500 ⁇ m.
• the support examples include metal drums, metal bands, glass plates, resin films, and metal foils.
• the support is preferably a glass plate or a resin film.
• the compound that is incompatible with the polymer having a glass transition temperature of 100° C. or higher is not particularly limited as long as it is a compound that can undergo phase separation when the membrane A is formed. preferable.
• Water-soluble in the present disclosure means that 0.1 g or more can be dissolved in 100 g of water at 25°C.
• the compound incompatible with the polymer having a glass transition temperature of 100° C. or higher may be a low-molecular-weight compound having a molecular weight of less than 1,000, or a high-molecular-weight compound having a weight-average molecular weight Mw of 1,000 or more. From the viewpoints of pore formation and easiness of elution, it is preferably a polymer compound having a weight average molecular weight Mw of 1,000 or more, and more preferably a water-soluble resin.
• Water-soluble resins include, for example, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, poly(N-vinylacetamide), water-soluble polyesters, and water-soluble polyurethanes.
• polyvinylpyrrolidone is preferable as the compound incompatible with the polymer.
• the solvent is not particularly limited as long as it can dissolve a polymer having a glass transition temperature of 100° C. or higher and a compound incompatible with a polymer having a glass transition temperature of 100° C. or higher.
• the immersion step is a step of forming a film B by immersing the film A in a coagulation bath.
• the component of the coagulation bath is not particularly limited, but from the viewpoint of coagulability and thermal conductivity, it is preferably water, a polar solvent, or a mixed solvent of water and a polar solvent.
• a mixed solvent of water and a polar solvent is more preferred, and water is particularly preferred.
• Polar solvents used in the coagulation bath include dioxane, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, cellosolves, methanol, ethanol, propanol, acetone, tetrahydrofuran, polyethylene glycol, and glycerin.
• the temperature of the coagulation bath is preferably 0°C to 50°C, more preferably 10°C to 35°C, and particularly preferably 20°C to 30°C, from the viewpoint of coagulability.
• the immersion time is not particularly limited, and can be selected as appropriate.
• the method for producing a polymer film according to the present disclosure preferably includes a step of applying gas to the film A after the casting step and before the immersion step. By adjusting the time for which the gas is applied, it is possible to adjust the average pore size of the obtained porous membrane on the side opposite to the support (also referred to as the air side).
• the gas is not particularly limited, but air is preferred.
• the temperature of the gas is preferably 0°C to 50°C, more preferably 10°C to 35°C, and particularly preferably 20°C to 30°C.
• the relative humidity of the gas is preferably 30% to 90%, more preferably 35% to 80%, particularly preferably 40% to 70%.
• the time for which the gas is applied is not particularly limited, and may be selected so as to obtain the desired average pore size.
• the method for producing a polymer film according to the present disclosure preferably includes a step of peeling the film B from the support during or after the immersion step. Stripping may be performed in the coagulation bath or outside the coagulation bath.
• the peeling method is not particularly limited, and a known method can be used.
• the temperature during peeling is not particularly limited, but is preferably 0°C to 50°C.
• the peeling speed is not particularly limited and can be selected as appropriate.
• the elution step is a step of eluting a compound incompatible with a polymer having a glass transition temperature of 100° C. or higher from membrane B to produce a porous membrane.
• a method of contacting the membrane B with the eluate is preferable, and a method of immersing the membrane B in the eluate is more preferable.
• the eluent may be a compound that does not dissolve the first polymer but dissolves a compound incompatible with the first polymer at a certain temperature. From the viewpoint of selective dissolution, a water-soluble solvent is preferable. .
• water-soluble solvents include glycerin, 1,2,6-hexanetriol, trimethylolpropane, alkanediols (e.g., ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1 ,3-butanediol, 1,4-butanediol, 2-butene-1,4-diol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 1,2-octane diol, 1,2-hexanediol, 1,2-pentanediol, 4-methyl-1,2-pentanediol, etc.), polyalkylene glycol (e.g., diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, di Polyhydric alcohols such as propylene glycol, polyoxyethylene polyoxypropan
• the water-soluble solvent is preferably polyhydric alcohol or polyhydric alcohol ether, more preferably polyhydric alcohol, still more preferably polyalkylene glycol, and particularly preferably diethylene glycol.
• the elution temperature in the elution step depends on the solubility of the first polymer, etc., and the boiling point and melting point of the eluate used, but is preferably 20°C to 150°C, and is preferably 50°C to 100°C. is more preferred, and 60°C to 90°C is particularly preferred.
• the elution time in the elution step is not particularly limited, but is preferably 0.1 minute to 24 hours, more preferably 0.5 minutes to 60 minutes, and particularly 1 minute to 10 minutes. preferable.
• the method for producing a polymer film according to the present disclosure preferably includes a step of washing the porous membrane after the elution step.
• the method for producing a polymer film according to the present disclosure preferably includes a step of drying the porous membrane after the elution step or after the step of washing the porous membrane.
• the washing liquid used for washing is not particularly limited, but is preferably water, a polar solvent, or a mixed solvent of water and a polar solvent, more preferably water or a mixed solvent of water and a polar solvent. Water is preferred, and water is particularly preferred.
• the washing temperature and washing time are not particularly limited and can be selected as appropriate. Also, the washing means is not particularly limited, and known washing means can be used.
• the drying temperature and drying time are not particularly limited and can be selected as appropriate.
• the drying means is not particularly limited, and known drying means can be used.
• the firing step is a step of firing the porous membrane.
• the firing temperature is not particularly limited, it is preferably 200°C to 400°C, more preferably 250°C to 300°C.
• the firing time is not particularly limited, it is preferably 0.1 to 5 hours, more preferably 2 to 4 hours.
• Firing is preferably carried out in an inert gas atmosphere.
• inert gases include nitrogen.
• the impregnation step is a step of impregnating the fired porous membrane with a second solution containing a compound having a functional group.
• the second dispersion may contain a solvent.
• the solvent is a polar solvent.
• Polar solvents include dioxane, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, cellosolves, methanol, ethanol, propanol, acetone, tetrahydrofuran, polyethylene glycol, and glycerin.
• the solvent is preferably N-methylpyrrolidone.
• the method for producing a polymer film according to the present disclosure preferably includes a step of heating the obtained polymer film after the impregnation step.
• the heating temperature and heating time are not particularly limited and can be selected as appropriate.
• the heating means is not particularly limited, and known heating means can be used.
• the curing reaction proceeds in the heating step after the impregnation step, resulting in the reaction product of the epoxy resin and the imidazole-based compound. is formed.
• a reaction product of an epoxy resin and an imidazole compound is a compound containing an NC bond.
• a first phase containing a polymer having a glass transition temperature of 100° C. or higher and a second phase containing an epoxy resin and an imidazole compound are mixed.
• -Applications- Polymer films according to the present disclosure can be used in a variety of applications. Among others, it can be suitably used for films for electronic parts such as printed wiring boards, and more suitably for flexible printed circuit boards.
• the polymer film according to the present disclosure can be suitably used as a polymer film for metal adhesion.
• the laminate according to the present disclosure may be a laminate including the polymer film according to the present disclosure.
• the laminate according to the present disclosure preferably has the polymer film according to the present disclosure and a layer arranged on at least one surface of the polymer film.
• the layer arranged on at least one surface of the polymer film is not particularly limited, and examples thereof include a polymer layer and a metal layer.
• the layer arranged on at least one surface of the polymer film may be a coating layer.
• the layer arranged on at least one surface of the polymer film may be arranged on the entire surface of the polymer film, or may be arranged only on a part of the polymer film.
• the laminate according to the present disclosure preferably has the polymer film according to the present disclosure and a metal layer or metal wiring arranged on at least one surface of the polymer film.
• the metal layer or metal wiring may be a known metal layer or metal wiring, but is preferably a copper layer or copper wiring, for example.
• a method for attaching the polymer film and the metal layer according to the present disclosure is not particularly limited, and a known lamination method can be used.
• the peel strength between the polymer film and the metal layer is preferably 0.5 kN/m or more, more preferably 0.7 kN/m or more, and is 0.7 kN/m to 2.0 kN/m. is more preferable, and 0.9 kN/m to 1.5 kN/m is particularly preferable.
• the peel strength between a polymer film and a metal layer shall be measured by the following method.
• a 1.0 cm wide peeling test piece was prepared from the laminate of the polymer film and the metal layer, the polymer film was fixed to a flat plate with double-sided adhesive tape, and a 50 mm The strength (kN/m) is measured when the polymer film is peeled from the metal layer at a speed of 1/min.
• the metal layer is preferably a copper layer.
• the copper layer is preferably a rolled copper foil formed by a rolling method or an electrolytic copper foil formed by an electrolytic method, and more preferably a rolled copper foil from the viewpoint of bending resistance.
• the average thickness of the metal layer preferably the copper layer
• the copper foil may be a carrier-attached copper foil that is detachably formed on a support (carrier).
• carrier A known carrier can be used.
• the average thickness of the carrier is not particularly limited, it is preferably 10 ⁇ m to 100 ⁇ m, more preferably 18 ⁇ m to 50 ⁇ m.
• etching it is also preferable to process the metal layer in the laminate according to the present disclosure into a desired circuit pattern by, for example, etching to form a flexible printed circuit board.
• the etching method is not particularly limited, and known etching methods can be used.
• Glass transition temperature (Tg) 5 mg of a sample was placed in a DSC measurement pan, and the temperature was raised from 30°C at 10°C/min in a nitrogen stream.
• LC-A liquid crystal polymer produced according to the following production method
• LC-B liquid crystal polymer produced according to the following production method
• the liquid crystalline polyester (B1) obtained above was heated from room temperature to 160° C. over 2 hours and 20 minutes in a nitrogen atmosphere, then from 160° C. to 180° C. over 3 hours and 20 minutes. The mixture was held for 5 hours for solid phase polymerization, cooled, and then pulverized with a pulverizer to obtain a powdery liquid crystalline polyester (B2).
• the flow initiation temperature of this liquid crystalline polyester (B2) was 220°C.
• the liquid crystalline polyester (B2) obtained above was heated in a nitrogen atmosphere from room temperature (23° C.) to 180° C. over 1 hour and 25 minutes, and then from 180° C. to 255° C. over 6 hours and 40 minutes. , and held at 255° C. for 5 hours for solid phase polymerization, followed by cooling to obtain a powdery liquid crystalline polyester (LC-A).
• the flow initiation temperature of the liquid crystalline polyester (LC-A) was 302°C. Further, the melting point of this liquid crystal polyester (LC-A) was measured using a differential scanning calorimeter, and the result was 311°C.
• the liquid crystalline polyester (B1) obtained above is held at 250° C. for 3 hours in a nitrogen atmosphere for solid phase polymerization, cooled, and then pulverized with a pulverizer to obtain a powdery liquid crystalline polyester ( LC-B) was obtained.
• PVP-A Polyvinylpyrrolidone (product name "Pitzcol K-50", manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used. PVP-A is a compound incompatible with LC-A at 0°C to 100°C.
• PSU-A Polysulfone (product name "Udel P-3500", manufactured by Solvay Japan Co., Ltd.) was used. PSU-A is a compound compatible with LC-A at 0°C to 100°C.
• SBR-A Styrene-butadiene rubber (product name "P1430-SBR", manufactured by General Science Corporation)
• A-1 Low dielectric loss tangent filler with an average particle size of 600 nm (specially treated fused spherical silica, manufactured by Denka Co., Ltd.)
• B-1 Aluminum nitride particles (particle size 1 ⁇ m type, manufactured by Tokuyama Co., Ltd.)
• C-1 Silica particles with an average particle size of 0.5 ⁇ m (product name “SO-C2”, manufactured by Admatechs Co., Ltd.)
• D-1 Hollow powder with an average particle size of 16 ⁇ m (product name “Glass Bubbles iM30K”, manufactured by 3M Japan Co., Ltd.)
• E-1 Boron nitride particles (product name “HP40MF100”, manufactured by Mizushima Ferroalloy Co., Ltd.)
• M-2 Epoxy resin (product name "YX8800", manufactured by Mitsubishi Chemical Corporation)
• Examples 1 to 7, Comparative Example 3 Preparation of polymer solution-
• the polymer shown in Table 1 was added to N-methylpyrrolidone and stirred at 140° C. for 4 hours under a nitrogen atmosphere to obtain a solution with a solid concentration of 18% by mass.
• 87 parts by mass of PVP-A, 7 parts by mass of lithium chloride, and 8 parts by mass of water were added to 100 parts by mass of the polymer and uniformly dissolved.
• a sintered fiber metal filter with a nominal pore size of 10 ⁇ m it was also passed through a sintered fiber filter with a nominal pore size of 10 ⁇ m to obtain a polymer solution.
• the film was heated in a nitrogen atmosphere at 280° C. for 3 hours to obtain a porous film (baking step).
• Impregnation The above M-1, 2-ethylmethylimidazole as a curing agent, and fillers shown in Table 1 were added and uniformly stirred to prepare an impregnating solution.
• the content of 2-ethylmethylimidazole was adjusted to 2 parts by mass with respect to 100 parts by mass of M-1.
• the amount of filler added was adjusted so as to be the amount shown in Table 1.
• no filler was added.
• the porous membrane was impregnated with the impregnation liquid (impregnation step). The impregnating liquid entered the pores formed in the porous membrane to form a phase containing the epoxy resin and 2-ethylmethylimidazole.
• phase 1 The phase containing LC-A, PSU-A, or SBR-A was designated Phase 1
• Phase 2 the phase containing the reaction product of the epoxy resin and 2-ethylmethylimidazole
• a copper foil (product name “3EC-M1S-HTE”, manufactured by Mitsui Kinzoku Co., Ltd., 12 ⁇ m) was placed on the polymer film of Examples 1 to 7 so that the roughened surface side was in contact with the polymer film.
• a laminator product name: "Vacuum Laminator V-130” manufactured by Nikko Materials Co., Ltd.
• lamination was performed for 1 minute under the conditions of 140° C. and a lamination pressure of 0.4 MPa.
• thermocompression machine product name “MP-SNL”, manufactured by Toyo Seiki Seisakusho Co., Ltd.
• thermocompression bonding is performed for 10 minutes at 300 ° C. and 4.5 MPa to form a laminate with copper foil. got It was confirmed that the laminate had a peel strength of 0.5 kN/m or more between the polymer film and the copper foil.
• Table 1 shows the elongation at break of the polymer films obtained in Examples and Comparative Examples. Also, the glass transition temperature of the polymer contained in the first phase is described.
• Examples 1 to 7 have a co-continuous structure (phase separation structure) containing at least two continuous phases, and the first phase is a polymer having a glass transition temperature of 100° C. or higher. and the second phase contains at least one compound selected from the group consisting of a compound having a functional group and a compound having a bond A, so that the polymer film has a high breaking elongation and high toughness. I found out. Moreover, the thermal conductivity of the films of Examples 2 and 3 was 4 W/(m ⁇ K) and 4 W/(m ⁇ K), respectively, which were excellent.

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